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The impact of 27 volatile organic compounds (VOCs) on the regional O3 increment was investigated using measurements made at the UK EMEP supersites Harwell (1999-2001 and 2010-2012) and Auchencorth (2012). Ozone at these sites is representative of rural O3 in southeast England and northern UK, respectively. The monthlydiurnal regional O3 increment was defined as the difference between the regional and hemispheric background O3 concentrations, respectively, derived from oxidant vs. NOx correlation plots, and cluster analysis of back trajectories arriving at Mace Head, Ireland. At Harwell, which had substantially greater regional O3 increments than Auchencorth, variation in the regional O3 increment mirrored afternoon depletion of anthropogenic VOCs due to photochemistry (after accounting for diurnal changes in boundary layer mixing depth, and weighting VOC concentrations according to their photochemical ozone creation potential). A positive regional O3 increment occurred consistently during the summer, during which time afternoon photochemical depletion was calculated for the majority of measured VOCs, and to the greatest extent for ethene and mCp-xylene. This indicates that, of the measured VOCs, ethene and mCp-xylene emissions reduction would be most effective in reducing the regional O3 increment but that reductions in a larger number of VOCs would be required for further improvement. The VOC diurnal photochemical depletion was linked to anthropogenic sources of the VOC emissions through the integration of gridded anthropogenic VOC emission estimates over 96 h air-mass back trajectories. This demonstrated that one factor limiting the effectiveness of VOC gridded emissions for use in measurement and modelling studies is the highly aggregated nature of the 11 SNAP (Selected Nomenclature for Air Pollution) source sectors in which they are reported, as monthly variation in speciated VOC trajectory emissions did not reflect monthly changes in individual VOC diurnal photochemical depletion. Additionally, the major VOC emission source sectors during elevated regional O3 increment at Harwell were more narrowly defined through disaggregation of the SNAP emissions to 91 NFR (Nomenclature for Reporting) codes (i.e. sectors 3D2 (domestic solvent use), 3D3 (other product use) and 2D2 (food and drink)). However, spatial variation in the contribution of NFR sectors to parent SNAP emissions could only be accounted for at the country level. Hence, the future reporting of gridded VOC emissions in source sectors more highly disaggregated than currently (e.g. to NFR codes) would facilitate a more precise identification of those VOC sources most important for mitigation of the impact of VOCs on O3 formation. In summary, this work presents a clear methodology for achieving a coherent VOC, regional-O3-impact chemical climate using measurement data and explores the effect of limited emission and measurement species on the understanding of the regional VOC contribution to O3 concentrations. [ABSTRACT FROM AUTHOR]

There is limited availability of long-term, high temporal resolution, chemically speciated aerosol measurements which can provide further insight into the health and environmental impacts of particulate matter. The Monitor for AeRosols and Gases (MARGA, Applikon B.V., NL) allows for the characterisation of the inorganic components of PM10 and PM2.5 (NHC4+, NO3-, SO2-4, Cl-, Na+, K+, Ca2+, Mg2+) and inorganic reactive gases (NH3, SO2, HCl, HONO and HNO3) at hourly resolution. The following study presents 6.5 years (June 2006 to December 2012) of quasi-continuous observations of PM2.5 and PM10 using the MARGA at the UK EMEP supersite, Auchencorth Moss, SE Scotland. Auchencorth Moss was found to be representative of a remote European site with average total water soluble inorganic mass of PM2.5 of 3.82 µgm-3. Anthropogenically derived secondary inorganic aerosols (sum of NHC 4, NO3- and nss-SO2-4) were the dominating species (63%) of PM2.5. In terms of equivalent concentrations, NH4+ provided the single largest contribution to PM2.5 fraction in all seasons. Sea salt was the main component (73%) of the PMcoarse fraction (PM10-PM2.5/, though NO3- was also found to make a relatively large contribution to the measured mass (17%) providing evidence of considerable processing of sea salt in the coarse mode. There was on occasions evidence of aerosol from combustion events being transported to the site in 2012 as high KC concentrations (deviating from the known ratio in sea salt) coincided with increases in black carbon at the site. Pollution events in PM10 (defined as concentrations >12 µgm-3) were on average dominated by NHC 4 and NO3-, where smaller loadings at the site tended to be dominated by sea salt. As with other western European sites, the charge balance of the inorganic components resolved were biased towards cations, suggesting the aerosol was basic or more likely that organic acids contributed to the charge balance. This study demonstrates the UK background atmospheric composition is primarily driven by meteorology with sea salt dominating air masses from the Atlantic Ocean and the Arctic, whereas secondary inorganic aerosols tended to dominate air masses from continental Europe. [ABSTRACT FROM AUTHOR]

Analyses have been undertaken of the trends and drivers of the distributions of ground-level O3 concentrations associated with potential impacts on human health and vegetation using measurements at the two UK EMEP supersites of Harwell and Auchencorth. These two sites provide representation of rural O3 over the wider geographic areas of south-east England and northern UK, respectively. The O3 exposures associated with health and vegetation impacts were quantified, respectively, by the SOMO10 and SOMO35 metrics, and by the flux-based PODγ metrics for wheat, potato, beech and Scots pine. Statistical analyses of measured O3 and NOx concentrations was supplemented by analyses of meteorological data and NOx emissions along air-mass back trajectories. The findings highlight the differing responses of impact metrics to the decreasing contribution of regional O3 episodes in determining O3 concentrations at Harwell between 1990 and 2013, associated with European NOx emission reductions. An improvement in human health-relevant O3 exposure observed when calculated by SOMO35, which decreased significantly, was not observed when quantified by SOMO10. The decrease in SOMO35 is driven by decreases in regionally-produced O3 which makes a larger contribution to SOMO35 than to SOMO10. For the O3 vegetation impacts at Harwell, no significant trend was observed for the PODγ metrics of the four species, in contrast to the decreasing trend in vegetation-relevant O3 exposure perceived when calculated using the crop AOT40 metric. The decreases in regional O3 production have not decreased PODγ as climatic and plant conditions reduced stomatal conductance and uptake of O3 during regional O3 production. Ozone concentrations at Auchencorth (2007-2013) were more influenced by hemispheric background concentrations than at Harwell. For health-related O3 exposures this resulted in lower SOMO35 but similar SOMO10 compared with Harwell; for vegetation PODγ values, this resulted in greater impacts at Auchencorth for vegetation types with lower exceedance ("Y") thresholds and longer growing seasons (i.e. beech and Scots pine). Additionally, during periods influenced by regional O3 production, a greater prevalence of plant conditions which enhance O3 uptake (such as higher soil water potential) at Auchencorth compared to Harwell resulted in exacerbation of vegetation impacts at Auchencorth, despite being further from O3 precursor emissions sources. These analyses indicate that quantifications of future improvement in health-relevant O3 exposure achievable from pan-European O3 mitigation strategies is highly dependent on the choice of O3 concentration cut-off threshold, and reduction in potential health impact associated with more modest O3 concentrations requires reductions in O3 precursors on a larger (hemispheric) spatial scale. Additionally, while further reduction in regional O3 is more likely to decrease O3 vegetation impacts within the spatial domains of Auchencorth compared to Harwell, larger reductions in vegetation impact could be achieved across the UK from reduction of hemispheric background O3 concentrations. [ABSTRACT FROM AUTHOR]

Surface concentrations of secondary inorganic particle components over the UK have been analysed for 2001-2010 using the EMEP4UK regional atmospheric chemistry transport model and evaluated against measurements. Gas/particle partitioning in the EMEP4UK model simulations used a bulk approach, which may lead to uncertainties in simulated secondary inorganic aerosol. However, model simulations were able to accurately represent both the long-term decadal surface concentrations of particle sulfate and nitrate and an episode in early 2003 of substantially elevated nitrate measured across the UK by the AGANet network. The latter was identified as consisting of three separate episodes, each of less than 1 month duration, in February, March and April. The primary cause of the elevated nitrate levels across the UK was meteorological: a persistent high-pressure system, whose varying location impacted the relative importance of transboundary versus domestic emissions. Whilst long-range transport dominated the elevated nitrate in February, in contrast it was domestic emissions that mainly contributed to the March episode, and for the April episode both domestic emissions and long-range transport contributed. A prolonged episode such as the one in early 2003 can have substantial impact on annual average concentrations. The episode led to annual concentration differences at the regional scale of similar magnitude to those driven by long-term changes in precursor emissions over the full decade investigated here. The results demonstrate that a substantial part of the UK, particularly the south and southeast, may be close to or exceeding annual mean limit values because of import of inorganic aerosol components from continental Europe under specific conditions. The results reinforce the importance of employing multiple year simulations in the assessment of emissions reduction scenarios on particulate matter concentrations and the need for international agreements to address the transboundary component of air pollution. [ABSTRACT FROM AUTHOR]

Gaseous elemental (GEM), particulate bound (PBM) and gaseous oxidised (GOM) mercury species were monitored between 2009 and 2011 at the rural monitoring site, Auchencorth Moss, Scotland using the Tekran speciation monitoring system. GEM average for the three year period was 1.40 ± 0.19 ng m³ which is comparable with other northern hemisphere studies. PBM and GOM concentrations are very low in 2009 and 2010 with geometric mean (x / ÷ standard deviation) PBM values of 2.56 (x / ÷ 3.44) and 0.03 (x / ÷ 17.72) pg m-3 and geometric mean (x / ÷ standard deviation) GOM values of 0.11 (x / ÷ 4.94) and 0.09 (x / ÷ 8.88) pg m-3 respectively. Using wind sector analysis and air mass back trajectories, the importance of local and regional sources on speciated mercury are investigated and we show the long range contribution to GEM from continental Europe, and that the lowest levels are associated with polar and marine air masses from the north west sector. [ABSTRACT FROM AUTHOR]

Leaf nitrogen and leaf surface area influence the exchange of gases between terrestrial ecosystems and the atmosphere, and play a significant role in the global cycles of carbon, nitrogen and water. The purpose of this study is to use field-based and satellite remote-sensing-based methods to assess leaf nitrogen pools in five diverse European agricultural landscapes located in Denmark, Scotland (United Kingdom), Poland, the Netherlands and Italy. REGFLEC (REGularized canopy reFLECtance) is an advanced image-based inverse canopy radiative transfer modelling system which has shown proficiency for regional mapping of leaf area index (LAI) and leaf chlorophyll (CHLl) using remote sensing data. In this study, high spatial resolution (10-20 m) remote sensing images acquired from the multispectral sensors aboard the SPOT (Satellite For Observation of Earth) satellites were used to assess the capability of REGFLEC for mapping spatial variations in LAI, CHL1 and the relation to leaf nitrogen (N1) data in five diverse European agricultural landscapes. REGFLEC is based on physical laws and includes an automatic model parameterization scheme which makes the tool independent of field data for model calibration. In this study, REGFLEC performance was evaluated using LAI measurements and non-destructive measurements (using a SPAD meter) of leaf-scale CHL1 and N1 concentrations in 93 fields representing crop- and grasslands of the five landscapes. Furthermore, empirical relationships between field measurements (LAI, CHL1 and N1) and five spectral vegetation indices (the Normalized Difference Vegetation Index, the Simple Ratio, the Enhanced Vegetation Index-2, the Green Normalized Difference Vegetation Index, and the green chlorophyll index) were used to assess field data coherence and to serve as a comparison basis for assessing REGFLEC model performance. The field measurements showed strong vertical CHL1 gradient profiles in 26% of fields which affected REGFLEC performance as well as the relationships between spectral vegetation indices (SVIs) and field measurements. When the range of surface types increased, the REGFLEC results were in better agreement with field data than the empirical SVI regression models. Selecting only homogeneous canopies with uniform CHL1 distributions as reference data for evaluation, REGFLEC was able to explain 69% of LAI observations (rmse=0.76), 46% of measured canopy chlorophyll contents (rmse=719 mgm-2) and 51% of measured canopy nitrogen contents (rmse=2.7 gm-2). Better results were obtained for individual landscapes, except for Italy, where REGFLEC performed poorly due to a lack of dense vegetation canopies at the time of satellite recording. Presence of vegetation is needed to parameterize the REGFLEC model. Combining REGFLEC- and SVI-based model results to minimize errors for a "snap-shot" assessment of total leaf nitrogen pools in the five landscapes, results varied from 0.6 to 4.0 t km-2. Differences in leaf nitrogen pools between landscapes are attributed to seasonal variations, extents of agricultural area, species variations, and spatial variations in nutrient availability. In order to facilitate a substantial assessment of variations in N1 pools and their relation to landscape based nitrogen and carbon cycling processes, time series of satellite data are needed. The upcoming Sentinel-2 satellite mission will provide new multiple narrowband data opportunities at high spatio-temporal resolution which are expected to further improve remote sensing capabilities for mapping LAI, CHL1 and N1. [ABSTRACT FROM AUTHOR]

Biogenic influences on the composition and characteristics of aerosol were investigated on Bird Island (54°00' S, 38°03' W) in the South Atlantic during November and December 2010. This remote marine environment is characterised by large seabird and seal colonies. The chemical composition of the submicron particles, measured by an aerosol mass spectrometer (AMS), was 21% non-sea salt sulfate 2% nitrate, 7% ammonium, 22% organics and 47% sea salt including sea salt sulfate. A new method to isolate the sea salt signature from the high-resolution AMS data was applied. Generally, the aerosol was found to be less acidic than in other marine environments due to the high availability of ammonia, from local fauna emissions. By positive matrix factorisation five different organic aerosol (OA) profiles could be isolated: an amino acids/amine factor (AA-OA, 18% of OA mass), a methanesulfonic acid OA factor (MSA-OA, 25 %), a marine oxygenated OA factor (M-OOA, 40 %), a sea salt OA fraction (SS-OA, 7 %) and locally produced hydrocarbon-like OA (HOA, 9 %). The AA-OA was dominant during the first two weeks of November and found to be related with the hatching of penguins in a nearby colony. This factor, rich in nitrogen (C :N ratio = 0.13), has implications for the biogeochemical cycling of nitrogen in the area as particulate matter is often transported over longer distances than gaseous N-rich compounds. The MSA-OA was mainly transported from more southerly latitudes where phytoplankton bloomed. The bloom was identified as one of three sources for particulate sulfate on Bird Island, next to sea salt sulfate and sulfate transported from South America. M-OOA was the dominant organic factor and found to be similar to marine OA observed at Mace Head, Ireland. An additional OA factor highly correlated with sea salt aerosol was identified (SS-OA). However, based on the available data the type of mixture, internal or external, could not be determined. Potassium was not associated to sea salt particles during 19% of the time, indicating the presence of biogenic particles in addition to the MSA-OA and AA-OA factors. [ABSTRACT FROM AUTHOR]

A comprehensive assessment of nitrogen (N) flows at the landscape scale is fundamental to understand spatial interactions in the N cascade and to inform the development of locally optimised N management strategies. To explore these interactions, complete N budgets were estimated for two contrasting hydrological catchments (dominated by agricultural grassland vs. semi-natural peat-dominated moorland), forming part of an intensively studied landscape in southern Scotland. Local scale atmospheric dispersion modelling and detailed farm and field inventories provided high resolution estimations of input fluxes. Direct agricultural inputs (i.e. grazing excreta, N2 fixation, organic and synthetic fertiliser) accounted for most of the catchment N inputs, representing 82% in the grassland and 62% in the moorland catchment, while atmospheric deposition made a significant contribution, particularly in the moorland catchment, contributing 38% of the N inputs. The estimated catchment N budgets highlighted areas of key uncertainty, particularly N2 exchange and stream N export. The resulting N balances suggest that the study catchments have a limited capacity to store N within soils, vegetation and groundwater. The "catchment N retention", i.e. the amount of N which is either stored within the catchment or lost through atmospheric emissions, was estimated to be 13% of the net anthropogenic input in the moorland and 61% in the grassland catchment. These values contrast with regional scale estimates: Catchment retentions of net anthropogenic input estimated within Europe at the regional scale range from 50% to 90%, with an average of 82% (Billen et al., 2011). This study emphasises the need for detailed budget analyses to identify the N status of European landscapes. [ABSTRACT FROM AUTHOR]

Leaf nitrogen and leaf surface area influence the exchange of gases between terrestrial ecosystems and the atmosphere, and they play a significant role in the global cycles of carbon, nitrogen and water. Remote sensing data from satellites can be used to estimate leaf area index (LAI), leaf chlorophyll (CHLl) and leaf nitrogen density (Nl). However, methods are often developed using plot scale data and not verified over extended regions that represent a variety of soil spectral properties and canopy structures. In this paper, field measurements and high spatial resolution (10-20m) remote sensing images acquired from the HRG and HRVIR sensors aboard the SPOT satellites were used to assess the predictability of LAI, CHLl and Nl. Five spectral vegetation indices (SVIs) were used (the Normalized Difference Vegetation index, the Simple Ratio, the Enhanced Vegetation Index-2, the Green Normalized Difference Vegetation Index, and the green Chlorophyll Index) together with the image-based inverse canopy radiative transfer modelling system, REGFLEC (REGularized canopy reFLECtance). While the SVIs require field data for empirical model building, REGFLEC can be applied without calibration. Field data measured in 93 fields within crop- and grasslands of five Euro- pean landscapes showed strong vertical CHLl gradient profiles in 20% of fields. This affected the predictability of SVIs and REGFLEC. However, selecting only homogeneous canopies with uniform CHLl distributions as reference data for statistical evaluation, significant (p < 0.05) predictions were achieved for all landscapes, by all methods. The best performance was achieved by REGFLEC for LAI (r² = 0.7; rmse=0.73), canopy chlorophyll content (r² = 0.51; rmse=439mg m-2 ) and canopy nitrogen con- tent (r² = 0.53; rmse=2.21 gm-2 ). Predictabilities of SVIs and REGFLEC simulations generally improved when constrained to single land use categories (wheat, maize, bar- ley, grass) across the European landscapes, reflecting sensitivity to canopy structures. Predictability further improved when constrained to local (10x10 km² ) landscapes, thereby reflecting sensitivity to local environmental conditions. All methods showed different predictabilities for land use categories and landscapes. Combining the best methods, LAI, canopy chlorophyll content (CHLc) and canopy nitrogen content (Nc) for the five landscapes could be predicted with improved accuracy (LAI rmse=0.59; CHLc rmse=346 gm-2; Nc rmse=1.49 gm-2 ). Remote sensing-based results showed that the vegetation nitrogen pools of the five agricultural landscapes varied from 0.6 to 4.0 tkm-2. Differences in nitrogen pools were attributed to seasonal variations, extents of agricultural area, species variations, and spatial variations in nutrient availability. Information on Nl and total Nc pools within the landscapes is important for the spatial evaluation of nitrogen and carbon cycling processes. The upcoming Sentinel-2 satellite mission will provide new multiple narrow-band data opportunities at high spatioemporal resolution which are expected to further improve remote sensing predictabilities of LAI, CHLl and Nl. [ABSTRACT FROM AUTHOR]

A comprehensive assessment of nitrogen (N) flows at the landscape scale is fundamental to understand spatial interactions in the N cascade and to inform the development of locally optimised N management strategies. To explore this interactions, complete N budgets were estimated for two contrasting hydrological catchments (dominated by agricultural grassland vs. semi-natural peat-dominated moorland), forming part of an intensively studied landscape in southern Scotland. Local scale atmospheric dispersion modelling and detailed farm and field inventories provided high resolution estimations of input fluxes. Agricultural inputs (i.e. grazing excreta, organic and synthetic fertiliser) accounted for most of the catchment N inputs with 80% in the grassland and 57% in the moorland catchment, while atmospheric deposition made a significant contribution, particularly in the moorland catchment with 38% of the N inputs. The estimated catchment N budgets highlighted areas of key uncertainty, particularly N2 emissions from denitrification and stream N export. The resulting N balances suggest that the study catchments have a limited capacity to store N within soils, vegetation and groundwater. The "catchment N retention", i.e. the amount of N which is either stored within the catchment or lost through atmospheric emissions, was estimated to be 3% of the net anthropogenic input in the moorland and 55% in the grassland catchment. These values contrast with regional scale estimates: catchment retentions of net anthropogenic input estimated within Europe at the regional scale range from 50% to 90% with an average of 82% (Billen et al., 2011). This study emphasises the need for detailed budget analyses to identify the N status of European landscapes. [ABSTRACT FROM AUTHOR]

The article discusses the inter-comparison of eleven instruments used for the measurement of atmospheric ammonia's ambient concentrations. It highlights the instruments deployed in the procedure which include ion mobility spectrometer (IMS), two Quantum Cascade Laser Absorption Spectrometers and a Chemical Ionisation Mass Spectrometer (CIMS). It reveals that the ammonia gas concentrations at the field between the instruments used were hourly average.

The phase transitions and hygroscopic growth of two humic acid aerosols (Aldrich sodium salt and Leonardite Standard (IHSS)) and their mixtures with ammonium sulphate have been investigated using a combination of two techniques, Fourier transform infra-red (FTIR) spectroscopy and tandem differential mobility analysis (TDMA). A growth factor of 1.16 at 85% relative humidity (RH) was found for the Aldrich humic acid which can be regarded as an upper limit for growth factors of humic-like substances (HULIS) found in atmospheric aerosol and is significantly smaller than that of typical atmospheric inorganics. We find that the humic acid aerosols exhibit water uptake over all relative humidities with no apparent phase changes, suggesting that these aerosols readily form supersaturated droplets. In the mixed particles, the humic acid component decreases the deliquescence relative humidity (DRH) and increases the efflorescence relative humidity (ERH) of the ammonium sulphate component, and there is some degree of water uptake prior to ammonium sulphate deliquescence. In addition, at low RH, the FTIR spectra show that the ammonium is present in a different chemical environment in the mixed aerosols than in crystalline ammonium sulphate, perhaps existing as a complex with the humic materials. The growth factors of the mixed aerosols are intermediate between those of the singlecomponent aerosols and can be predicted assuming that the inorganic and organic fractions take up water independently. [ABSTRACT FROM AUTHOR]

The phase transitions and hygroscopic growth of two humic acid aerosols (Aldrich sodium salt and Leonardite Standard (IHSS)) and their mixtures with ammonium sulphate have been investigated using a combination of two techniques, Fourier transform infra-red (FTIR) spectroscopy and tandem differential mobility analysis (TDMA). A growth factor of 1.16 at 85% relative humdity (RH) was found for the Aldrich humic acid which can be regarded as an upper limit for growth factors of humic-like substances (HULIS) found in atmospheric aerosol and is significantly smaller than that of typical atmospheric inorganics. We find that the humic acid aerosols exhibit water uptake over all relative humidites with no apparent phase changes, suggesting that these aerosols readily form supersaturated droplets. In the mixed particles, the humic acid component decreases the deliquescence relative humidity (DRH) and increases the efflorescence relative humidity (ERH) of the ammonium sulphate component, and there is some degree of water uptake prior to ammonium sulphate deliquescence. In addition, at low RH, the FTIR spectra show that the ammonium is present in a different chemical environment in the mixed aerosols than in crystalline ammonium sulphate, perhaps existing as a complex with the humic materials. The growth factors of the mixed aerosols are intermediate between those of the single component aerosols and can be predicted assuming that the inorganic and organic fractions take up water independently. [ABSTRACT FROM AUTHOR]

The heterogeneous chemistry of HOI, ICl and IBr on sea salt and sea salt proxies has been studied at 274 K using two experimental approaches: a wetted wall flow tube coupled to an electron impact mass spectrometer (WWFT-MS) and an aerosol flow tube (AFT) coupled to a differential mobility analyser (DMA) and a chemical ionisation mass spectrometer (CIMS). Uptake of all three title molecules into bulk aqueous halide salt films was rapid and controlled by gas phase diffusion. Uptake of HOI gave rise to gas-phase ICl and IBr, with the latter being the predominant product whenever Br(-) was present. Only partial release of IBr was observed due to high solubility of dihalogens in the film. ICl uptake gave the same yield of IBr as HOI uptake. Uptake of ICl on NaBr aerosol was accommodation limited with alpha = 0.018 +/- 0.004 and gas phase IBr product has a yield of 0.6 +/- 0.3. The results show that HOI can act as a catalyst for activation of bromine from sea-salt aerosols in the marine boundary layer, via the reactions: HOI(aq) + Cl + H--> ICl(aq) + H(2)O(l) and ICl(aq) + Br--> IBr(aq) + Cl.